KR20150004342A - Gypsum dispersant - Google Patents

Gypsum dispersant Download PDF

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KR20150004342A
KR20150004342A KR20147028420A KR20147028420A KR20150004342A KR 20150004342 A KR20150004342 A KR 20150004342A KR 20147028420 A KR20147028420 A KR 20147028420A KR 20147028420 A KR20147028420 A KR 20147028420A KR 20150004342 A KR20150004342 A KR 20150004342A
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gypsum
polymer
mono
acid
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KR20147028420A
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아키라 이케다
세이이치 코시사카
카츠토시 사토
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도호 가가꾸 고오교 가부시키가이샤
요시노 셋고 가부시키가이샤
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/28Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/281Polyepoxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/24Epihalohydrins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40Surface-active agents, dispersants
    • C04B2103/408Dispersants
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

[과제] 품질이 상이한 원료석고를 사용해도 석고 슬러리의 유동성의 개선효과가 우수하고, 또한, 석고 슬러리의 경화지연을 발생시키지 않는, 석고용 분산제 및 석고용 첨가제를 제공하는 것이다. [Problem] The quality improving effect of fluidity of the gypsum slurry also uses a different raw material gypsum excellent, and further, to do not cause delayed curing of the gypsum slurry, the dispersing agent employed provides a seat and seat employ additives.
[해결수단] (A)폴리카르본산계 중합체와, (B)알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체를 함유하는 것을 특징으로 하는 석고용 분산제이다. [MEANS FOR SOLVING PROBLEMS] (A) the polycarboxylic acid-based polymer, (B) employed seats, characterized in that it contains a polymer obtained by alkylene diamines and / or mono-amines and reaction with the high gave as an essential component to be epi a dispersant.

Description

석고용 분산제{GYPSUM DISPERSANT} Seats employment dispersants {GYPSUM DISPERSANT}

본 발명은 석고보드 등의 각종 석고성형물을 제조할 때에, 석고 및 물로 이루어지는 석고 슬러리의 유동성 개선을 목적으로 첨가되는 석고용 분산제에 관한 것이다. The present invention relates to a seat employing dispersing agent in the production of various molded articles, such as gypsum plasterboard, it added for the purpose of improving the fluidity of the gypsum slurry comprising gypsum and water.

석고보드는 주로 건축용의 내장재료로서, 방화성, 차음성, 단열성이 우수한 특성을 갖고, 또한 저렴하기 때문에, 널리 사용되고 있다. Because drywall is primarily an internal material of construction, having a fire resistance, sound insulation, is excellent in heat insulating properties, and low cost, is widely used. 석고보드는 일반적으로는 유입성형방법으로 제조되고, 소석고, 물, 분산제, 기타 첨가제로 이루어지는 석고 슬러리와 발포 폼을 혼합기로 교반하고 혼합한 것을 원지에 흘려 끼우고, 두께와 폭을 조정한 후, 경화, 절단, 건조시켜 얻어진다. Gypsum board is generally sheathed flow to the base paper to a is made of a incoming molding method, stirring a gypsum slurry and a foam made of a calcined gypsum, water, dispersants, and other additives to the mixer and mixed, and then adjusting the thickness and width, curing is obtained by cutting and drying. 석고보드로는 보통보드, 경질보드, 강화보드, 화장보드 등의 종류가 있으며, 각각의 보드의 요구특성에 따라, 첨가제의 종류, 조합량, 강화재의 첨가 등이 달라지지만, 제조방법은 동일하다. And the type of gypsum board are typically boards, hard boards, reinforced boards, make-up board or the like, depending on the required characteristics of each board, the type of additive, addition of the combined amount, reinforcements, etc. varies, the production method is the same .

상기 석고 슬러리 제작시에 이용되는 분산제는, 석고보드의 원지에 대한 전성을 높이는 목적으로 사용되는 것 외에, 슬러리 제작시의 단위수분량을 저감하여 건조효율을 높이고, 성형보드의 밀도를 높여 고강도 보드를 얻는 목적으로도 사용되고 있다. In addition to the dispersing agent used at the time of the gypsum slurry produced is used for the purpose of increasing the conductivity of the base paper of the plaster boards, to reduce the unit water content during the slurry production to increase the drying efficiency, increasing the density of the molding board, the high strength board It obtaining also used for the purpose.

종래, 석고용의 분산제로는, 포름알데히드를 원료로 하는 나프탈렌설폰산염 포름알데히드 축합물, 멜라민설폰산염 포름알데히드 축합물, 및, 비스페놀류와 아미노벤젠설폰산의 포름알데히드 축합물 등의 화합물이 널리 사용되어 왔다(특허문헌 1 및 특허문헌 2 참조). Conventionally, the dispersing agent of the seat employed is a compound such as formaldehyde to naphthalene sulfonate formaldehyde condensate to a raw material, a melamine sulfonate formaldehyde condensate, and a formaldehyde condensate of bisphenol and aminobenzene sulfonic acid is widely It has been used (see Patent Document 1 and Patent Document 2).

또한 특허문헌 3에는, 폴리카르본산계의 분산제를 석고 수성조성물에 함유시킴으로써, 높은 플로우값과 우수한 셀프 레벨링성을 갖는 셀프 레벨링성 석고 수성조성물을 이루는 것이 제안되어 있다. In addition, Patent Document 3, a polycarboxylic acid-based dispersing agent of the gypsum by including in the aqueous composition, it is proposed to form a high flow value and self-leveling with excellent self-leveling property gypsum aqueous composition.

나아가, 특허문헌 4에는, 아미드기, 아미노기 및 이미노기로부터 선택되는 질소원자함유의 구조단위와, 카르본산기를 갖는 구조단위와, 폴리알킬렌글리콜기를 갖는 구조단위를 포함하고, 중합에 의해 얻어진 수용성 양성고분자화합물을 주성분으로 하는 것을 특징으로 하는 석고용 분산제가 제안되어 있다. Further, Patent Document 4, an amide group, an amino group and to those already structural unit of a nitrogen atom selected from the group, a carboxylic acid and a structural unit having a polyalkylene glycol comprising a structural unit having a group, and the aqueous obtained by polymerization the seat employ dispersants, characterized in that the amphoteric polymer compounds containing as a main component has been proposed. 그러나, 원료석고에 포함되는 불순물의 영향에 의해 효과가 안정적으로 발현되지 않는 경우가 있어, 개량이 요구되고 있었다. However, there are cases that the effect due to the influence of impurities contained in the gypsum material is not stably expressed and had been improved is required.

일본특허 제3067811호 공보 Japanese Patent No. 3067811 discloses 일본특허 제3733821호 공보 Japanese Patent No. 3733821 discloses 일본특허공고 S64-1426호 공보 Japanese Patent Publication No. S64-1426 일본특허공개 2007-320786호 공보 Japanese Unexamined Patent Application Publication 2007-320786 discloses

일반적으로, 상술한 지금까지 제안된 폴리카르본산계 분산제는 pH 등의 사용조건을 적절히 선택함으로써, 석고 슬러리에 대하여 우수한 분산성능을 발현할 수 있지만, 동시에 경화지연도 일으키게 되어, 결과적으로 석고보드의 생산성을 저하시키는 문제를 안고 있었다. In general, the polycarboxylic acid-based dispersant proposed above now will by appropriately selecting the conditions for the use of the pH, etc., are, but can exhibit an excellent dispersibility, causing at the same time curing a delay with respect to the gypsum slurry, resulting in a gypsum board It had faced the problem of lowering productivity.

또한, 석고원료는 다양하며, 수입되는 천연석고, 발전소나 정련소의 탈황장치로부터 배출되는 배연탈황석고, 인산석고, 불산석고 등의 부산석고, 석고보드 폐재로부터 분리회수된 리사이클석고 등이 수송비용의 저감화를 도모하는 목적으로 공장마다 구분하여 사용되고 있다. In addition, the gypsum raw materials vary, and the imported natural gypsum, flue gas discharged from the desulfurization apparatus of the power plant or refinery gas desulfurization gypsum, phosphoric acid, gypsum, and separate from the Busan plaster, plaster board waste materials, such as hydrofluoric acid gypsum recovered recycled gypsum such as the transportation cost for the purpose of promoting the reduction is used separately for each plant. 이에 따라 석고에 포함되는 불순물 등도 각 공장에서 상이하며, 그 영향으로 석고용 감수제의 성능을 충분히 발휘할 수 없는 상황이 생기고 있다. Accordingly, also impurities contained in the plaster differ from each plant, and there occurs a situation that can not sufficiently exhibit the performance of the seat reducing agent employed in its effects.

본 발명은, 상기의 사정을 감안하여 이루어진 것으로서, 그 해결하고자 하는 과제는, 품질이 상이한 원료석고를 사용해도 석고 슬러리의 유동성의 개선효과가 우수하고, 또한, 석고 슬러리의 경화지연을 발생시키지 않는, 석고용 분산제 및 석고용 첨가제를 제공하는 것에 있다. The present invention, been made in view of the circumstances described above, a problem to be the resolution is, the quality improvement of the flow effect of the FIG gypsum slurry using a different raw material gypsum excellent, and further, does not cause a hardening retardant in the gypsum slurry , to provide a seat and hire dispersant additives seats employment.

본 발명자는, 상기의 과제를 해결하기 위하여 예의연구를 행한 결과, 본 발명을 발견하기에 이르렀다. The present inventors, leading to did strenuous research to solve the above result, found the present invention.

즉 본 발명은, (A)폴리카르본산계 중합체와, (B)알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체를 함유하는 것을 특징으로 하는 석고용 분산제에 관한 것이다. That is, the present invention, (A) the polycarboxylic acid-based polymer, (B) alkylene-diamines and / or mono-amines and seat characterized in that it contains a polymer obtained by reacting to a high gave as an essential component to be epi It relates to employment dispersants.

본 발명은 또한, 석고 슬러리의 유동성을 개선하는 것을 목적으로 배합되는, 알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체로 이루어지는 석고용 첨가제에 관한 것이다. The present invention also relates to a seat employing the additive comprising a polymer obtained by reacting to a high gave as an essential component to be compounded for the purpose of improving the fluidity of the gypsum slurry, alkylene diamines and / or mono-amines and to epi .

본 발명의 석고용 분산제는, (A)폴리카르본산계 중합체와, (B)알킬렌디아민류와 에피할로하이드린의 반응생성물을 병용함으로써, 품질이 상이한 원료석고를 사용해도, 그 종류에 상관없이 충분한 유동성을 안정적으로 부여할 수 있다. Analysis employed a dispersant of the present invention, (A) in the polycarboxylic acid-based polymer, (B) an alkylene diamine and by a combination of the reaction product of a high gave to be epitaxially, also, those types of quality with the different raw gypsum sufficient fluidity, no matter can be stably acquired.

그리고 상기 석고용 분산제를 석고 슬러리에 함유시킴으로써, 생산성을 저하시키지 않고 석고보드를 제조할 수 있다. And by including the three dispersants employed in the gypsum slurry, it is possible to produce a gypsum board without lowering the productivity.

이하에 본 발명에 대하여 상세하게 설명한다. It will be described in detail the present invention are described below.

상기 (A)폴리카르본산계 중합체로는, 폴리알킬렌글리콜계 불포화단량체(a)에서 유래하는 구성단위와, 불포화카르본산계 단량체(b)에서 유래하는 구성단위를 갖는 중합체를 바람직하게 사용할 수 있다. The (A) in the polycarboxylic acid-based polymer is polyalkylene glycol and structural units derived from the unsaturated monomer (a), unsaturated carboxylic acid monomer (b) can be preferably used a polymer having a structural unit derived from a have.

폴리알킬렌글리콜계 불포화단량체(a)에서 유래하는 구성단위로는, 하기 일반식(2)로 표시할 수 있다. A structural unit derived from a polyalkylene glycol unsaturated monomer (a) is to can be represented by the general formula (2).

[화학식 1] Formula 1

Figure pct00001

(식 중, R 6 , R 7 , R 8 , R 9 는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 22의 탄화수소기를 나타내고, X는 -COO- 또는 -(CH 2 ) a O-를 나타내고, a는 1 내지 20의 정수를 나타낸다. AO는 탄소원자수 2 내지 4의 알킬렌옥시기를 나타낸다. n은 알킬렌옥시기의 부가몰수로 1 내지 200의 수를 나타낸다.) (Wherein, R 6, R 7, R 8, R 9 each independently represents a hydrogen atom or a hydrocarbon group of 1 to 22 carbon atoms, X is -COO- or - (CH 2) a represents an O-, a represents an integer of 1 to 20. AO represents an alkylene oxide of 2 to 4 carbon atoms. n is a number of from 1 to 200 to the addition mole number of the alkylene group.)

상기 식(2)에 있어서, R 6 , R 7 , R 8 , R 9 는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 22의 탄화수소기를 나타내고, 바람직하게는 수소원자 또는 탄소원자수 1 내지 8의 알킬기, 보다 바람직하게는 수소원자, 메틸기, 에틸기, 프로필기, 부틸기이다. In the formula (2), R 6, R 7, R 8, R 9 each independently represents a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 22, and preferably a hydrogen atom or an alkyl group carbon atom number of 1 to 8, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group.

AO는 탄소원자수 2 내지 4의 알킬렌옥시기를 나타내고, 구체적으로는 에틸렌옥시기, 프로필렌옥시기, 부틸렌옥시기를 들 수 있다. AO represents an alkylene oxide of 2 to 4 carbon atoms, specifically there may be mentioned an ethylene group, a propylene group, a butylene oxy. 2종 이상의 알킬렌옥시기로 구성되는 경우, 이들 알킬렌옥시기는 블록 부가 또는 랜덤 부가 중 어느 것이어도 된다. When configured as two kinds or more of alkylene oxide, these alkylene groups are may be either block addition or random addition.

n은 상기 알킬렌옥시기의 부가몰수로 1 내지 200의 수를 나타낸다. n is a number of from 1 to 200 to the number of moles of the alkyleneoxy group. 바람직하게는 5 내지 120, 보다 바람직하게는 10 내지 100, 더욱 바람직하게는 40 내지 100이다. Preferably from 5 to 120, more preferably 10 to 100, more preferably from 40 to 100.

폴리알킬렌글리콜계 불포화단량체(a)로는, 구체적으로는 이하의 것을 예시할 수 있다. Roneun polyalkylene glycol unsaturated monomer (a), specifically, there can be mentioned the following.

메톡시폴리에틸렌글리콜모노(메트)아크릴레이트, 메톡시{폴리에틸렌글리콜(폴리)프로필렌글리콜}모노(메트)아크릴레이트, 에톡시폴리에틸렌글리콜모노(메트)아크릴레이트, 에톡시{폴리에틸렌글리콜(폴리)프로필렌글리콜}모노(메트)아크릴레이트, 프로폭시폴리에틸렌글리콜모노(메트)아크릴레이트, 프로폭시{폴리에틸렌글리콜(폴리)프로필렌글리콜}모노(메트)아크릴레이트, 부톡시폴리에틸렌글리콜모노(메트)아크릴레이트, 부톡시{폴리에틸렌글리콜(폴리)프로필렌글리콜}모노(메트)아크릴레이트 등의 알콕시폴리알킬렌글리콜모노(메트)아크릴레이트; Methoxy polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol in } mono (meth) acrylate, propoxy polyethylene glycol mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, butoxy polyethylene glycol mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol} alkoxy polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylate; 비닐알코올알킬렌옥사이드 부가물, (메트)알릴알코올알킬렌옥사이드 부가물, 3-부텐-1-올알킬렌옥사이드 부가물, 이소프렌알코올(3-메틸-3-부텐-1-올)알킬렌옥사이드 부가물, 3-메틸-2-부텐-1-올알킬렌옥사이드 부가물, 2-메틸-3-부텐-2-올알킬렌옥사이드 부가물, 2-메틸-2-부텐-1-올알킬렌옥사이드 부가물, 2-메틸-3-부텐-1-올알킬렌옥사이드 부가물 등의 불포화알코올폴리알킬렌글리콜 부가물. Vinyl alcohol alkylene oxide adducts, (meth) allyl alcohol alkylene oxide adducts, 3-buten-1-ol alkylene oxide adducts, isoprene alcohol (3-methyl-3-buten-1-ol) alkylene oxide adducts, 3-methyl-2-buten-1-ol alkylene oxide adducts, 2-methyl-3-butene-2-ol alkylene oxide adducts, 2-methyl-2-buten-1-ol alkylene oxide adducts, 2-methyl-3-buten-1-ol alkylene oxide addition unsaturated alcohol polyalkylene glycol adduct, such as water. 또한 본 발명에서는, (메트)아크릴레이트란 아크릴레이트와 메타크릴레이트의 양방을 말하고, (메트)알릴알코올이란 알릴알코올과 메타릴알코올의 양방을 말한다. In the present invention, (meth) acrylate is to say both the acrylate and methacrylate, (meth) allyl alcohol refers to both the allyl alcohol and meta reel alcohol.

상기 불포화카르본산계 단량체(b)로는, 구체적으로는, 아크릴산, 메타크릴산, 말레산, 푸마르산, 이타콘산 및 불포화지방산 그리고 이들의 산무수물, 예를 들어 무수말레산을 나타낸다. Roneun the unsaturated carboxylic acid monomer (b), specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and unsaturated fatty acids and acid anhydrides thereof, for example represents a maleic anhydride. 이 중, 특히 메타크릴산이 바람직하다. Of these, particularly acid methacrylate is preferred.

폴리카르본산계 중합체(A)에 있어서, 상기 단량체(a), (b) 이외에 공중합 가능한 단량체(c)로는, 이하의 공지의 단량체를 들 수 있다; Roneun polycarboxylic acid-based polymer according to (A), the monomer (a), (b) copolymerizable monomer in addition to (c) as possible, can be given in the following well-known monomers; (1) (비)수계 단량체류: 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, 스티렌 등; (1) (non) aqueous monomers: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, styrene; (2) 음이온계 단량체류: 비닐설폰산염, 스티렌설폰산염, 메타크릴산인산에스테르 등; (2) anionic monomers: vinyl sulfonic acid, styrene sulfonic acid salt, methacrylic acid esters and the like; (3) 아미드계 단량체류: 아크릴아미드, 아크릴아미드의 알킬렌옥사이드 부가물 등, (4) 폴리아미드폴리아민계 단량체: 폴리아미드폴리아민과 (메트)아크릴산의 축합물에, 필요에 따라 알킬렌옥사이드를 부가한 화합물. (3) amide-based monomers include: acrylamide, such as acrylamide, alkylene oxide adducts, (4) a polyamide polyamine-based monomer: polyamide polyamine and (meth) condensation product of acrylic acid, an alkylene oxide, as needed adding the compound.

상기 단량체(a) 내지 (c)의 공중합비는 질량기준으로 (a):(b):(c)=50~95:5~50:0~40이 바람직하고, (a):(b):(c)=70~90:10~30:0~20이 보다 바람직하다. The monomer (a) to a copolymerization ratio by mass of (c) (a) :( b) :( c) = 50 ~ 95: 5 ~ 50: 0 ~ 40 :( b are preferred, and (a)) : (c) = 70 ~ 90: 10 ~ 30: 0 ~ 20 is more preferable.

상기 (A)폴리카르본산계 중합체의 제조방법으로는, 특별히 한정되지 않고, 예를 들어, 중합개시제를 이용한 용액중합이나 괴상중합 등의 공지의 중합방법을 사용할 수 있다. As the (A) polycarboxylic production process of the base polymer is not particularly limited, and for example, can be used a known polymerization method such as solution polymerization or bulk polymerization using a polymerization initiator. 또한 분자량은 특별히 한정되지 않지만, 중량평균 분자량(겔침투크로마토그래피법, 폴리에틸렌글리콜 환산)으로 5,000 내지 100,000의 범위에 있는 것이, 양호한 분산성 발현의 관점에서 바람직하다. In addition, the molecular weight is not particularly limited, it is preferable in terms of the weight average molecular weight be in the range of 5,000 to 100,000 with (gel permeation chromatography method, in terms of polyethylene glycol), good dispersibility expression.

또한, 상기 (A)폴리카르본산계 중합체는, 수산화리튬, 수산화칼륨, 수산화나트륨, 암모니아, 알킬아민, 유기아민류 등의 중화제에 의해, 미리 부분중화, 혹은 완전중화된 형태로서, 본 발명의 석고용 분산제에 함유되는 것이 바람직하다. Further, the (A) the polycarboxylic acid-based polymer, lithium hydroxide, as, partially neutralized in advance, or fully neutralized form by a neutralizing agent such as potassium hydroxide, sodium hydroxide, ammonia, alkylamines, organic amines, three of the present invention to be included in an amount to employ a dispersing agent is preferred.

상기 (B)알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체에 대하여, 이하에 설명한다. With respect to the polymer obtained by reacting to a high it gave as an essential component in the (B) alkylene-diamines and / or mono amine with epi to be described below.

상기 알킬렌디아민류로는, 하기 일반식(1)로 표시되는 것이 바람직하게 이용된다. With the alkylene diamine is preferably used is represented by the following general formula (1).

[화학식 2] [Formula 2]

Figure pct00002

(식 중, R 1 , R 2 는 탄소원자수 1 내지 5의 알킬기 혹은 탄소원자수 1 내지 4의 하이드록시알킬기를 나타내고, R 3 , R 4 는 수소원자 또는 탄소원자수 1 내지 5의 알킬기 혹은 탄소원자수 1 내지 4의 하이드록시알킬기를 나타내고, R 5 는 탄소원자수 2 내지 6의 알킬렌기를 나타낸다.) (Wherein, R 1, R 2 represents a hydroxy alkyl group having carbon atoms of 1 to 5 alkyl groups or carbon atoms of 1 to 4, R 3, R 4 is a hydrogen atom or a carbon atom number of 1 to 5 alkyl groups or carbon atoms of 1 to represents a hydroxy alkyl group of 4, R 5 represents an alkylene group of 2 to 6 carbon atoms.)

구체적으로는 디메틸아미노에틸아민, 디에틸아미노에틸아민, 디메틸아미노프로필아민, 디에틸아미노프로필아민, 3-메틸아미노프로필아민, N,N,N',N'-테트라메틸에틸렌디아민, N,N,N',N'-테트라에틸에틸렌디아민, N,N,N',N'-테트라메틸프로필렌디아민, N,N,N',N'-테트라에틸프로필렌디아민, N,N,N',N'-테트라하이드록시에틸에틸렌디아민, N,N-디메틸-N',N'-디하이드록시에틸프로필렌디아민, 디에틸아미노4-아미노펜탄, 테트라메틸헥사메틸렌디아민, 테트라메틸1,3-부탄디아민, 테트라메틸페닐렌디아민 등을 들 수 있고, 그 중에서도 디메틸아미노프로필아민, 디에틸아미노프로필아민이 바람직하다. Specifically, dimethylamino ethylamine, diethylamino-ethylamine, dimethylamino propylamine, diethylamino propylamine, 3-dimethylaminopropyl amine, N, N, N ', N'- tetramethylethylenediamine, N, N , N ', N'- tetraethyl ethylene diamine, N, N, N', N'- tetramethyl propylene diamine, N, N, N ', N'- tetraethyl propylene diamine, N, N, N', N '- tetra-hydroxyethyl ethylene diamine, N, N- dimethyl -N', N'- di-hydroxyethyl propylene diamine, 4-diethylamino acetaminophen Tan, tetramethyl hexamethylene diamine, tetramethyl-1,3-butanediamine , and the like tetra-phenyl diamine, of these, dimethylamino propylamine, diethylamino-propylamine are preferred.

상기 모노아민류로는, 구체적으로는, 메틸아민, 디메틸아민, 에틸아민, 디에틸아민, n-프로필아민, 디n-프로필아민, 이소프로필아민, 디이소프로필아민, n-부틸아민, 디n-부틸아민, s-부틸아민, 디s-부틸아민, t-부틸아민, 디t-부틸아민, 헥실아민, 디헥실아민, 시클로헥실아민, 디시클로헥실아민, 2에틸헥실아민, 디(2에틸헥실)아민 등의 알킬기를 갖는 모노아민류, 알릴아민, 디알릴아민 등의 알케닐기를 갖는 모노아민류, 모노에탄올아민, 디에탄올아민, 하이드록시프로필아민, 디하이드록시프로필아민, N-메틸에탄올아민, 아미노안식향산 등의 하이드록시알킬기를 갖는 모노아민류, 아닐린, 디페닐아민 등의 페닐기를 갖는 모노아민류, 벤질아민, 디벤질아민 등의 벤질기를 갖는 모노아민류, 암모니아 등을 들 수 있다. To the mono-amines, specifically, methylamine, dimethylamine, ethylamine, diethylamine, n- propylamine, di-n- propylamine, diisopropylamine, di-isopropylamine, n- butylamine, di-n - butylamine, s- butyl amine, di-butylamine s-, t- butylamine, di-t- butyl amine, hexyl amine, di-hexylamine, cyclohexylamine, dicyclohexylamine, 2-ethylhexylamine, di (2 ethylhexyl) mono amine, mono-ethanol amine, diethanol amine, hydroxypropyl amine, hydroxypropyl di-amine, N- methylethanolamine having an alkenyl group of mono amine, allylamine, diallylamine, etc. having an alkyl group such as an amine may include mono amines, ammonia or the like having an amine, mono-amine having a hydroxy alkyl group, such as amino acid, aniline, mono-di-amines having a phenyl group such as phenylamine, benzylamine, dibenzylamine, benzyl group of the.

상기 알킬렌디아민류 및 모노아민류는, 어느 한쪽으로부터 1종 또는 2종 이상을 선택하여 사용할 수도 있고, 양방으로부터 1종 또는 2종 이상을 선택하여 조합하여 사용할 수도 있다. The alkylene diamine, and mono-amines, may be selected individually or in combination of two or more from either side, can also be used in combination by selecting one or two or more from both.

또한, 상기 에피할로하이드린으로는, 에피클로로하이드린, 에피브로모하이드린, 메틸에피클로로하이드린 등을 들 수 있고, 이들을 단독으로 또는 2종 이상을 이용할 수 있다. Further, as to be the epi gave high, the epichlorohydrin may be mentioned high gave, such as epi-bromo high gave, it gave methyl epichlorohydrin high, can be used alone or two or more of them. 이들의 에피할로하이드린류 중에서도, 에피클로로하이드린이 가장 바람직하다. Among these gave a high current to be epitaxial, epichlorohydrin is most preferred.

상기 알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린의 반응몰비는 2:1~1:2의 범위로 하는 것이 바람직하다. The alkylene diamines and / or mono-amines and the reaction molar ratio of the high gave to be epitaxially 2: preferably in a range of 2: 1 to 1. 이 범위내의 몰비로 반응시키면, 얻어지는 중합체가 적당한 점도를 갖는 분자량의 것이 되며, 양호한 분산성이 얻어진다. Is reacted in a molar ratio within this range, the resulting polymer will be a molecular weight having an appropriate viscosity is obtained having good dispersibility. 이 중합체의 중량평균 분자량은 통상 1,000~1,000,000이지만, 바람직하게는 2,000~500,000, 보다 바람직하게는 3,000~100,000이다. The weight average molecular weight of the polymer, but is usually 1,000 to 1,000,000, preferably from 2,000 to 500,000, more preferably 3,000 to 100,000.

상기 (A)와 (B)의 비율은 특별히 한정되지 않지만, 질량비로 (A):(B)=1:1~30:1이면 바람직하고, 2:1~20:1이면 보다 바람직하다. The content of the (A) and (B) is not particularly limited, the mass ratio (A) :( B) = 1: 1 ~ 30: 1 is preferred, and 2:01 to 20:01 and more preferably is.

본 발명의 석고용 분산제가 석고 슬러리에 정상적으로 유동성을 주는 이유는 명백하지는 않지만, 분산제의 기능발휘를 저해하는 원료석고 중의 불순물에 (B)성분이 선택적으로 흡착하기 때문이라고 추측하고 있다. The reason analysis employed a dispersant of the present invention is that the flow normally in the gypsum slurry While not apparent, it is surmised that the component (B) of impurities in the raw gypsum to inhibit the function of the dispersant is exerted because it selectively adsorbs. 따라서, (B)성분을 석고용 첨가제로서, (A)성분 이외의 분산제, 예를 들어 리그닌설폰산염, 나프탈렌설폰산포르말린고축합물염, 멜라민설폰산포르말린고축합물염, 폴리스티렌설폰산염, 수용성비닐공중합체 등과 함께 사용할 수도 있다. Accordingly, (B) component of a seat employing additives, (A) a dispersing agent other than the ingredient, such as lignin sulfonates, naphthalenesulfonic acid-formaldehyde high condensate mulyeom, a melamine sulfonic acid-formaldehyde high condensate mulyeom, polystyrene sulfonate salt, a water-soluble vinyl Aerial It may be used along with the polymer.

본 발명의 석고용 분산제는, 원료석고에 대하여 통상 0.01~5질량%(분산제 고형분 질량비)를 첨가하고 사용될 수 있다. Seat of the present invention employ dispersants, it may be added 0.01 to 5% by weight (solid content weight ratio of dispersant) For the raw gypsum to be used. 분산제의 첨가방법은 여러가지가 있지만 석고와 혼합하기 전의 물에 희석하고 첨가하여 석고 슬러리를 제작하는 방법이 일반적이다. Method of addition of the dispersing agent is a general method which is different, but diluted with water prior to mixing with the plaster and is added making the gypsum slurry. 또한, (A)성분과 (B)성분은 미리 혼합하여 첨가할 수도 있고, 혼합하지 않고 각각 첨가할 수도 있다. Further, (A) component and the (B) component may be added to pre-mix may be added, without mixing, respectively. 각각 첨가하는 경우는 그 첨가순서는 어느 것이어도 된다. If the respective addition of the addition order is be any.

석고는 무수석고, 반수석고, 이수석고 등이 있다. The anhydrite gypsum is, half of the plaster, and the like yisuseok. 원료석고로는, 천연석고 또는 중화석고 혹은 부산석고 등의 화학석고를 단독으로, 혹은 이들의 2종 이상을 혼합한 것을 사용할 수 있다. Raw gypsum into ;, alone the chemical gypsum such as natural gypsum or neutralized gypsum or plaster, Pusan, or may be used by mixing two or more of them. 주된 화학석고로는 인산석고, 불산석고, 티탄석고 또는 배연탈황석고 등이 예시된다. As the major chemical gypsum plaster acid, hydrofluoric acid gypsum, plaster or the like are exemplified titanium FGD gypsum. 또한, 원료석고에는, 리사이클석고를 포함할 수도 있다. In addition, the gypsum raw material, there may comprise a recycled gypsum. 리사이클석고는, 석고보드 메이커로 자가 발생하는 폐석고보드, 신축시 및 해체시에 발생하는 폐석고보드 등으로부터 회수되는 리사이클석고이면 어느 것이어도 된다. Recycled gypsum, recycled gypsum is recovered from pyeseokgo board to self-generate a gypsum board manufacturer, pyeseokgo board, etc. generated at the time of expansion and contraction during and dismantling is be any. 본 발명의 석고용 분산제는 이들 중 어느 원료석고에 대해서도 호적하게 이용할 수 있고, 또한 여러가지 비율로 블렌드된 것에 대해서도 우수한 효과가 얻어진다. Analysis employed a dispersant of the present invention can be obtained an excellent effect also to the one can be used suitably even for any raw plaster of these, and blends with various ratios.

본 발명의 석고용 분산제와 함께 석고보드용 등에 사용되는 첨가제로는 범용감수제, 알킬황산염, 알킬에테르황산염, 알킬설폰산염 등의 포제, 소포제, 정포제, 경화조정제, 발수제, 접착제, 지연제 등이 있으며, 나아가 강화섬유로서 유리섬유, 탄소섬유, 파지(古紙), 원목 펄프(virgin pulp) 등을 첨가하거나, 혹은, 경량골재인 퍼라이트, 발포 스티롤 등과 함께 석고보드를 제작하는 것도 행해진다. Additives used in a plaster board with the three employment dispersant of the present invention is a general-purpose water-reducing agent, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates such as Posay, anti-foaming agent, foam stabilizer, a curing control agent, water repellent, adhesive, a retarder, etc. it may, further as the reinforcing fibers to produce a gypsum board, along with glass fibers, carbon fibers, gripping (古 紙), the addition of such as wood pulp (virgin pulp), or, a lightweight aggregate peorayiteu, foamed plastic is performed.

또한, 본 발명의 분산제를 도포하여 마무리에 이용하는 석고용 플라스터에 적용하는 것도 또한 용이하게 이룰 수 있다. Furthermore, also applicable to seats for use in the employment of plaster finish by applying a dispersing agent of the present invention also can be readily achieved.

실시예 Example

이하, 본 발명을 구체예를 들어 설명하는데, 본 발명은 이들 예에 한정되는 것은 아니다. Hereinafter to describe the present invention contains a specific example, the present invention is not limited to these examples. 또한, 공중합비, 혼합비는 특별히 언급하지 않는 한 질량기준이다. In addition, the copolymerization ratio, the mixing ratio is a weight basis unless otherwise specified.

[(A)폴리카르본산계 중합체] [(A) the polycarboxylic acid-based polymer;

본 실시예에서 이용한 (A)폴리카르본산계 중합체를 이하에 나타낸다. Used in this example (A) shows a polycarboxylic acid-based polymer described below.

<A1> (a1)폴리에틸렌글리콜(46몰)모노메틸에테르의 메타크릴산에스테르와 (b1)메타크릴산의 공중합물((a1):(b1)=9:1; 중량평균 분자량 25,000) <A1> (a1), polyethylene glycol (46 mole) of monomethyl ester of methacrylic acid and (b1) methacrylic acid copolymer ((a1) :( b1) of the ether = 9: 1; the weight average molecular weight 25,000)

<A2> (a2)폴리에틸렌글리콜(90몰)모노메틸에테르의 메타크릴산에스테르와, (b1)메타크릴산과, (c1)폴리아미드폴리아민계 단량체의 공중합물((a1):(b1):(c1)=77:13:10; 중량평균 분자량 44,000; 일본특허공개 2007-320786호 공보에 기재된 실시예 2의 공중합체) <A2> (a2) polyethylene glycol (90 mol) and the monomethyl ether methacrylate ester, (b1) methacrylic acid, (c1), a polyamide copolymer of a polyamine-based monomer ((a1) :( b1) :( c1) = 77: 13: 10; weight average molecular weight 44,000; the copolymer of example 2 described in Japanese Patent Application Publication No. 2007-320786)

<A3> (a3)3-메틸-3-부텐-1-올50EO2PO 부가물과 (b2)푸마르산의 공중합물((a3):(b2)=8:2; 중량평균 분자량 30,000) <A3> (a3) ​​3- methyl-3-buten-1-ol 50EO2PO adduct and (b2) copolymers of fumaric acid ((a3) :( b2) = 8: 2; average molecular weight 30,000)

[(B)아민류와 에피할로하이드린의 중합체의 제조] [(B) Preparation of the High gave polymer with an amine and be epitaxially;

본 실시예에서 이용한 알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린의 반응생성물(B1~B11)을 이하의 순서로 제조하였다. The reaction product (B1 ~ B11) gave a high alkylene diamines and / or mono amine with epi to using in this example was prepared according to the following procedures.

<분자량 측정조건> <Molecular Weight Measurement Conditions>

칼럼: OHpacSB-806MHQ, OHpacSB-804HQ, OHpacSB-803HQ(Showa Denko KK제) Column: OHpacSB-806MHQ, OHpacSB-804HQ, OHpacSB-803HQ (Showa Denko KK claim)

용리액: 0.5M 아세트산 질산나트륨수용액 Eluent: 0.5M acetic acid aqueous solution of sodium nitrate

검출기: 시차굴절계 Detector: Differential refractometer

검량선: 풀루란 기준 Calibration curve: standard pullulan

합성예 1 Synthesis Example 1

4구 플라스크에 N,N,N',N'-테트라메틸에틸렌디아민 116g(1몰)과 물 171g을 투입하고, 잘 혼합하였다. In a four-necked flask, N, N, N ', N'- tetramethylethylenediamine 116g (1 mole) and 171g of water, and mixed well. 이어서 35% 염산 94g(0.9몰)을 40℃ 이하에서 서서히 첨가하고, 아민의 염산염을 조제하였다. It was then slowly added to 35% hydrochloric acid and 94g (0.9 mole) below 40 ℃ to prepare a hydrochloride of an amine. 그 후, 온도를 70℃로 승온하고, 에피클로로하이드린 83.3g(0.9몰)을 약 2시간에 걸쳐 적하하였다. Then, the temperature was raised to 70 ℃, and the epichlorohydrin 83.3g (0.9 mol) was added dropwise over a period of about 2 hours. 그 동안, 온도는 70~80℃로 유지하였다. In the meantime, the temperature was maintained at 70 ~ 80 ℃. 에피클로로하이드린 적하종료후, 동일온도에서 6시간 반응을 속행하고, 중합체 B1의 50질량% 수용액을 얻었다. After epichlorohydrin was dropped terminated, the follow-up 6 hours at the same temperature to obtain a 50 mass% aqueous solution of polymer B1. 얻어진 중합체의 중량평균 분자량은 223,000이었다. The weight average molecular weight of the obtained polymer was 223,000.

합성예 2 Synthesis Example 2

합성예 1과 동일한 방법으로 N,N-디메틸-N',N'-디하이드록시에틸프로필렌디아민 190g(1몰)과 에피클로로하이드린 88g(0.95몰)을 반응시키고, 중합체 B2의 50질량% 수용액을 얻었다. The same method as in Example 1 with N, N- dimethyl -N ', N'- di-hydroxyethyl propylenediamine 190g (1 mol) of epichlorohydrin was reacted with the high gave 88g (0.95 mole) of 50% by weight of the polymer B2 a solution. 얻어진 중합체의 중량평균 분자량은 125,000이었다. The weight average molecular weight of the obtained polymer was 125,000.

합성예 3 Synthesis Example 3

합성예 1과 동일한 방법으로 N,N,N',N'-테트라하이드록시에틸에틸렌디아민 236g(1몰)과 에피클로로하이드린 92.5g(1몰)을 반응시키고, 중합체 B3의 50질량% 수용액을 얻었다. The same method as in Example 1 with N, N, N ', N'- tetra-hydroxyethyl ethylenediamine 236g (1 mol) of epichlorohydrin was reacted with 92.5g (1 mole), 50% by weight aqueous solution of polymer B3 It was obtained. 얻어진 중합체의 중량평균 분자량은 573,000이었다. The weight average molecular weight of the obtained polymer was 573,000.

합성예 4 Synthesis Example 4

합성예 1과 동일한 방법으로 N,N,N',N'-테트라하이드록시에틸에틸렌디아민 236g(1몰)과 에피클로로하이드린 50.9(0.55몰)를 반응시키고, 중합체 B4의 50질량% 수용액을 얻었다. The N, N, N ', N'- tetra-hydroxyethyl ethylenediamine 236g (1 mol) of epichlorohydrin and the reaction 50.9 (0.55 mol), 50% by weight of the polymer solution B4 in the same manner as in Synthesis Example 1 obtained. 얻어진 중합물의 중량평균 분자량은 63,000이었다. The weight average molecular weight of the obtained polymer was 63,000.

합성예 5 Synthesis Example 5

4구 플라스크에 디에틸아미노에틸아민 116g(1몰)과 물 196g을 투입하고, 잘 혼합하였다. Four-necked flask, diethyl aminoethyl amine 116g (1 mole) and added to 196g of water, and mixed well. 온도를 40~50℃로 유지하면서 에피클로로하이드린 88g(0.95몰)을 약 2시간에 걸쳐 적하하였다. The temperature of epichlorohydrin 88g (0.95 moles) while maintaining the 40 ~ 50 ℃ was added dropwise over a period of about 2 hours. 적하종료후, 동일온도에서 1시간, 추가로 70~80℃에서 8시간 반응을 속행시키고, 중합체 B5의 50질량% 수용액을 얻었다. After the addition, continue for one hour, additional 8 hours at 70 ~ 80 ℃ to the same temperature and, to obtain a 50% by weight aqueous solution of polymer B5. 얻어진 중합체의 중량평균 분자량은 21,000이었다. And a weight-average molecular weight of the resulting polymer was 21,000.

합성예 6 Synthesis Example 6

합성예 5와 동일한 방법으로 디메틸아미노프로필아민 102g(1몰)과 에피클로로하이드린 92.5g(1몰)을 반응시키고, 중합체 B6의 50질량% 수용액을 얻었다. Reacting in the same manner as in Synthesis Example 5 gave dimethylaminopropylamine 102g (1 mol) and epichlorohydrin high 92.5g (1 mole), and to give a 50% by weight aqueous solution of polymer B6. 얻어진 중합체의 중량평균 분자량은 35,000이었다. And a weight-average molecular weight of the resulting polymer was 35,000.

합성예 7 Synthesis Example 7

합성예 5와 동일한 방법으로 디메틸아미노프로필아민 102g(1몰)과 에피클로로하이드린 55.5g(0.6몰)을 반응시키고, 중합체 B7의 50질량% 수용액을 얻었다. Synthesis Example 5 and allowed to react for dimethylaminopropylamine 102g (1 mol) and epichlorohydrin 55.5g (0.6 mol) in the same manner to obtain a 50 mass% aqueous solution of the polymer B7. 얻어진 중합물의 중량평균 분자량은 5,300이었다. And a weight-average molecular weight of the obtained polymer was 5,300.

합성예 8 Synthesis Example 8

합성예 5와 동일한 방법으로 디메틸아민 45.1g(1몰)과 에피클로로하이드린 92.5g(1몰)을 반응시키고, 중합체 B8의 50질량% 수용액을 얻었다. Reacting in the same manner as in Synthesis Example 5 gave dimethyl amine 45.1g (1 mole) of epichlorohydrin high 92.5g (1 mole), and to obtain a 50 mass% aqueous solution of the polymer B8. 얻어진 중합체의 중량평균 분자량은 620,000이었다. The weight average molecular weight of the obtained polymer was 620,000.

합성예 9 Synthesis Example 9

합성예 5와 동일한 방법으로 디메틸아민 45.1g(1몰)과 에피클로로하이드린 46.3g(0.5몰)을 반응시키고, 중합체 B9의 50질량% 수용액을 얻었다. Synthesis Example 5 was reacted with the same method as dimethylamine 45.1g (1 mole) of epichlorohydrin and 46.3g (0.5 mole), to obtain a 50 mass% aqueous solution of the polymer B9. 얻어진 중합물의 중량평균 분자량은 6,600이었다. And a weight-average molecular weight of the obtained polymer was 6,600.

합성예 10 Synthesis Example 10

합성예 5와 동일한 방법으로 디메틸아민 22.6g(0.5몰)과 디메틸아미노프로필아민 51g(0.5몰)과 에피클로로하이드린 92.5g(1몰)을 반응시키고, 중합체 B10의 50질량% 수용액을 얻었다. Reacting 92.5g (1 mole) in the same manner as in Synthesis Example 5 gave dimethyl amine 22.6g (0.5 mol) of dimethylaminopropylamine 51g (0.5 mol) of epichlorohydrin was high to obtain a 50 mass% aqueous solution of the polymer B10. 얻어진 중합체의 중량평균 분자량은 960,000이었다. The weight average molecular weight of the obtained polymer was 960,000.

합성예 11 Synthesis Example 11

합성예 5와 동일한 방법으로 디메틸아민 22.6g(0.5몰)과 디메틸아미노프로필아민 51g(0.5몰)과 에피클로로하이드린 46.3g(0.5몰)을 반응시키고, 중합체 B11의 50질량% 수용액을 얻었다. Synthesis Example 5 was reacted with the same method as dimethylamine 22.6g (0.5 mol) of dimethylaminopropylamine 51g (0.5 mol) of epichlorohydrin 46.3g (0.5 mole), to obtain a 50 mass% aqueous solution of the polymer B11. 얻어진 중합체의 중량평균 분자량은 9,000이었다. The weight average molecular weight of the obtained polymer was 9,000.

표 1에 성능시험에서 이용한 원료석고의 조성을 나타낸다. It shows the composition of the raw gypsum used in the performance test in Table 1.

표 2에 나타낸 조성비율로 실시예 1~51 및 비교예 1~3의 석고용 분산제를 조제하고, 석고 분산성과 석고경화 지연성을 이하의 시험방법으로 시험하였다. Prepared in Examples 1 to 51 and Comparative Examples 1 to 3 seats of dispersant employed in the composition ratio shown in Table 2, were tested for dispersibility and gypsum plaster hardening retardant property test method as described below.

[표 1] TABLE 1

Figure pct00003

또한, No.6의 소석고로서 시판품인 Yoshino Gypsum Co.,Ltd.제의 Sakura-jirushi 소석고 A급을 이용하였다. In addition, we use the Sakura-jirushi Plaster A class of. The Yoshino Gypsum Co., Ltd as the commercially available product of the calcined gypsum No.6.

[성능시험] [Performance Test]

<석고 분산성> <Plaster dispersion>

표 2(표 2-1 및 표 2-2)에 나타낸 (A)성분 및 (B)성분을 이 표에 나타낸 배합비(질량비)로 혼합한 실시예 1~51, 비교예 1~3의 각 석고용 분산제를, 고형분 기준으로 0.18g(대 석고 0.06질량%)이 되도록 칭량하고, 물을 첨가하여 총량 195g이 되도록 반죽수(練り水)를 조정하였다. Table 2 (Table 2-1 and Table 2-2) In a mixture of the indicated components (A) and (B) component in the blending ratio (mass ratio) shown in the Table in Examples 1 to 51 and Comparative Examples Each of the seats 1-3 the dispersing agent employed, weighed to a solids basis with 0.18g (0.06 mass% for gypsum), and adjusting the number of dough so that the total amount of 195g was added to water (練 り 水). 이것에 표 1에 나타낸 배합조성의 소석고 또는 시판의 소석고(No.6) 300g을 첨가하고(수석고비 65%), 소형 쥬서믹서로 10초간 혼합을 행하였다. To this was added the calcined gypsum or calcined gypsum (No.6) 300g of commercially available formulated compositions shown in Table 1 were subjected to mixing for 10 seconds with (senior high boiling 65%), small juicer mixer.

우레탄제 보드(35cm×35cm) 중앙에 상부내경 75mm, 하부내경 85mm, 높이 40mm의 원통형 중공통을 사전에 준비하고, 혼합을 행한 석고 슬러리를 용기(원통형 중공통)가 가득해질 때까지 즉시 유입하였다. When the central urethane board (35cm × 35cm) be prepared for a cylindrical hollow tube of the upper internal diameter 75mm, bottom inner diameter 85mm, height 40mm in advance, and is full of container (a cylindrical hollow tube) the gypsum slurry subjected to mixing was immediately introduced to the . 그 후 중공통을 우레탄보드와 수직인 방향으로 인상하고, 석고 슬러리의 확대를 측정하였다. After raising the hollow tube a polyurethane board and the perpendicular direction, and to measure the expansion of the gypsum slurry. 확대의 최대로 보이는 직경과 그것과 수직인 직경을 측정하고, 그 평균값을 분산성의 지표로 하였다. Measuring the diameter and its perpendicular diameter to a maximum look-up of, and the average value was used as an index of dispersibility.

얻어진 결과(직경의 평균값)를 표 2(표 2-1 및 표 2-2)에 나타낸다. The results obtained (mean value of the diameter) shown in Table 2 (Table 2-1 and Table 2-2).

[석고경화 지연성] [Plaster hardening retardant property;

분산성 시험과 마찬가지로, 실시예 1~51, 비교예 1~3의 각 석고용 분산제를 고형분 기준으로 0.18g(대 석고 0.06질량%)이 되도록 정칭하고, 반죽수를 첨가하고 합계 195g이 되도록 조정하였다. Dispersibility test and similarly, in Examples 1 to 51 and Comparative Example 1 refers to the information 0.18g (0.06% by weight for plaster) each employ three dispersants based on solids of 1-3, adjusted to be added to the dough and the total 195g It was. 이것에 표 1에 나타낸 배합조성의 소석고 또는 시판의 소석고(No.6) 300g을 첨가하고(수석고비 65%), 소형 쥬서믹서로 10초간 혼합을 행하였다. To this was added the calcined gypsum or calcined gypsum (No.6) 300g of commercially available formulated compositions shown in Table 1 were subjected to mixing for 10 seconds with (senior high boiling 65%), small juicer mixer.

혼합후, 완성된 석고 슬러리를 즉시 종이컵으로 옮기고, 이것에 디지털온도계를 꽂아, 석고의 경화에 수반하는 발열온도를 10초 단위로 측정하고, 최대온도에 도달한 시간을 승온피크시간으로 하고, 경화지연성의 지표로 하였다. After mixing, transfer the completed gypsum slurry as soon as a paper cup, insert a digital thermometer On the other hand, measure the exothermic temperature caused by the hardening of the gypsum in 10 second increments, and the temperature was raised to the time taken to reach a maximum temperature at the peak time and curing delay indicators were in the castle.

얻어진 결과(승온피크시간)를 표 2(표 2-1 및 표 2-2)에 나타낸다. The results obtained (heating peak time) shown in Table 2 (Table 2-1 and Table 2-2).

[표 2] TABLE 2

Figure pct00004

[표 3] TABLE 3

Figure pct00005

표 2(표 2-1, 표 2-2)에 나타낸 바와 같이, 실시예 1 내지 51의 각 석고용 분산제를 첨가한 석고 슬러리는, 품질이 상이한 원료석고여도 우수한 분산성을 나타냄과 동시에, 경화지연성이 억제되어 있다고 하는 결과가 얻어졌다. Table 2 (Table 2-1, Table 2-2) in Example 1 to each seat gypsum slurry added with a dispersant employed 51 as shown in, at the same time the quality is different raw gypsum even shows excellent dispersibility, hardening the result of that is delayed can be suppressed is obtained.

한편, 아민과 에피할로하이드린의 축합물을 이용하지 않는 비교예 1 내지 3에서는, 시판품인 No.6의 소석고를 이용한 경우에는 실시예와 동일 정도의 결과를 나타내는 것도 있었지만, 실제 석고보드 제조에 있어서 공장에서 여러 가지의 석고를 블렌드하고 사용하는 것을 상정한 No.1~No.5의 소석고에서는, 분산성, 경화지연성 모두 실시예에 비해 열등한 결과가 되었다. On the other hand, the amine and which does not use a condensate Comparative Examples 1 to 3 gave in to the high-epi, when a commercially available product, there were also calcined gypsum of No.6 showing the results of the same degree as in Example, physical gypsum board manufacturing the inferior results compared to the calcined gypsum in a No.1 ~ No.5 assumed that blends a number of the plaster in the factory and used, both the dispersion and the curing was delayed embodiments in.

Claims (7)

  1. (A)폴리카르본산계 중합체와, (B)알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체를 함유하는 것을 특징으로 하는 석고용 분산제. (A) and the polycarboxylic acid-based polymer, (B) alkylene-diamines and / or mono-amines and analysis employed a dispersant comprising a polymer obtained by reacting to a high gave as an essential component to be epitaxially.
  2. 제1항에 있어서, According to claim 1,
    상기 알킬렌디아민류가, 하기 일반식(1)로 표시되는 것인, 석고용 분산제. Wherein the alkylene diamine is, to be represented by the general formula (1), seats employed dispersants.
    [화학식 1] Formula 1
    Figure pct00006

    (식 중, R 1 , R 2 는 탄소원자수 1 내지 5의 알킬기 혹은 탄소원자수 1 내지 4의 하이드록시알킬기를 나타내고, R 3 , R 4 는 수소원자 또는 탄소원자수 1 내지 5의 알킬기 혹은 탄소원자수 1 내지 4의 하이드록시알킬기를 나타내고, R 5 는 탄소원자수 2 내지 6의 알킬렌기를 나타낸다.) (Wherein, R 1, R 2 represents a hydroxy alkyl group having carbon atoms of 1 to 5 alkyl groups or carbon atoms of 1 to 4, R 3, R 4 is a hydrogen atom or a carbon atom number of 1 to 5 alkyl groups or carbon atoms of 1 to represents a hydroxy alkyl group of 4, R 5 represents an alkylene group of 2 to 6 carbon atoms.)
  3. 제1항에 있어서, According to claim 1,
    상기 알킬렌디아민류가 디알킬아미노알킬아민인, 석고용 분산제. The alkylene diamine is dialkylaminoalkyl amine, seats employed dispersants.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, The method according to any one of claims 1 to 3,
    상기 (A)폴리카르본산계 중합체가, 폴리알킬렌글리콜계 불포화단량체(a)에서 유래하는 구성단위와, 불포화카르본산계 단량체(b)에서 유래하는 구성단위를 갖는 것인, 석고용 분산제. Wherein (A) the polycarboxylic acid-based polymer is a polyalkylene glycol and structural units derived from the unsaturated monomer (a), unsaturated carboxylic having a structural unit derived from the acid monomer (b), seats employed dispersants.
  5. 제4항에 있어서, 5. The method of claim 4,
    상기 폴리알킬렌글리콜계 불포화단량체(a)에서 유래하는 구성단위가, 하기 일반식(2)로 표시되는 것인, 석고용 분산제. In that the structural unit derived from the polyalkylene glycol unsaturated monomer (a), represented by the general formula (2), seats employed dispersants.
    [화학식 2] [Formula 2]
    Figure pct00007

    (식 중, R 6 , R 7 , R 8 , R 9 는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 22의 탄화수소기를 나타내고, X는 -COO- 또는 -(CH 2 ) a O-를 나타내고, a는 1 내지 20의 정수를 나타낸다. AO는 탄소원자수 2 내지 4의 알킬렌옥시기를 나타낸다. n은 알킬렌옥시기의 부가몰수로 1 내지 200의 수를 나타낸다.) (Wherein, R 6, R 7, R 8, R 9 each independently represents a hydrogen atom or a hydrocarbon group of 1 to 22 carbon atoms, X is -COO- or - (CH 2) a represents an O-, a represents an integer of 1 to 20. AO represents an alkylene oxide of 2 to 4 carbon atoms. n is a number of from 1 to 200 to the addition mole number of the alkylene group.)
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, The method according to any one of claims 1 to 5,
    상기 (A)성분과 (B)성분의 비율이, 질량비로 (A):(B)=1:1~30:1인, 석고용 분산제. The component (A) and (B) the proportion of the ingredient in a mass ratio (A) :( B) = 1: 1 ~ 30: 1 person, seats employed dispersants.
  7. 알킬렌디아민류 및/또는 모노아민류와 에피할로하이드린을 필수성분으로 하여 반응시킴으로써 얻어지는 중합체로 이루어지는 석고용 첨가제. Alkylene-diamines and / or mono-amines and analysis employed the additive comprising a polymer obtained by reacting to a high gave as an essential component to be epitaxially.
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